基于阳极氧化铝模板增强NaYF4:Yb3+/Er3+上转换发光研究

慕立鹏; 周姚; 赵建行; 王丽; 蒋礼; 周见红

doi:10.7498/aps.73.20231405

摘要

采用共沉淀法制备了Yb³⁺/Er³⁺ 共掺杂的稀土掺杂上转换纳米晶. 并对样品的相结构和形貌进行表征. 结果表明: 制备的NaYF₄:Yb³⁺, Er³⁺具有六方晶相, 形貌均一. 利用两步阳极氧化法制备了阳极氧化铝模板. 通过扫描电子显微镜对样品形貌进行表征, 结果表明: 制备的阳极氧化铝模板周期性良好, 孔径均一. 在近红外 980 nm 激发下, 阳极氧化铝模板实现了对上转换纳米晶发光强度的增强, 使NaYF₄:Yb³⁺, Er³⁺的红绿光发射强度分别增强了4.4倍和9.0倍. 运用时域有限差分法探究其增强机制, 结果表明主要增强机制为阳极氧化铝模板的局域表面等离子共振效应. 接着探究了不同入射角度下模板的发光强度, 发现随着入射角度的增大, 上转换纳米晶红绿光的发光强度均先减小后增大. 本研究为上转换纳米晶在防伪领域和太阳能电池领域的应用提供了参考.

关键词:

Abstract

Up-conversion nanoparticle (UCNP) can collect near-infrared (NIR) light and convert it into visible light. Therefore, UCNP has potential applications in fields such as biomedicine, anti-counterfeiting, and solar cells. However, the efficiency of traditional UCNP in the above-mentioned fields is relatively low, greatly limiting its use in related fields. Therefore, enhancing the up-conversion luminescence intensity of up-conversion nanoparticles is particularly important and urgently needed. In this work, anodic alumina templates are used to enhance the luminescence intensity of up-conversion nanocrystals. NaYF₄:Yb³⁺, Er³⁺with a diameter of 35 nm is prepared by using co-precipitation method. Single pass AAO templates with pore size and pore spacing of 88 nm and 100 nm are prepared by using two-step anodization method. Finally, NaYF₄:Yb³⁺, Er³⁺/AAO composite structures are formed by using spin coating method. The red green light emission intensity of NaYF₄:Yb³⁺, Er³⁺/AAO sample can increase 4.4 and 9.0 times that of NaYF₄:Yb³⁺, Er³⁺/Al reference sample, respectively. The enhancement mechanism is explored by using the finite difference time domain method, and the results show that the primary source of enhancement is the localized surface plasmon resonance effect of the pores in the anodic alumina template. At the same time, the relationship between the up-conversion luminescence intensity of NaYF₄:Yb³⁺, Er³⁺/AAO sample and the incident angle is investigated. The experimental results show that as the incident angle increases, the luminescence intensity of the red and green light of NaYF₄:Yb³⁺, Er³⁺/AAO samples first decrease and then increase. Due to the coupling of the local surface plasmon resonance with the excitation wavelength and emission wavelength, the up-conversion luminescence intensity of the sample can be affected. The relationship of AAO channel enhancement factor with incident angle at excitation wavelength and emission wavelength is studied by using the finite difference time domain method. The results indicate that as the incident angle increases, the enhancement factor at the excitation wavelength decreases, while the enhancement factor at the emission wavelength increases after being illuminated at an incident angle of 15°. Therefore, when the incident angle is less than 20°, the electric field intensity at 980 nm dominates, but when it is greater than 20°, the electric field intensity at 540 nm and 650 nm takes precedence. The above results provide a reference for putting them into practical applications in the fields of anti-counterfeiting and solar cells.

Keywords:

作者及机构信息

1.
长春理工大学光电工程学院, 长春　130022

2.
长春理工大学, 光电测量和光信息传输技术教育部重点实验室, 长春　130022

3.
中国科学院化学研究所, 北京分子科学国家研究中心, 北京　100190

通信作者: 周见红, zjh@cust.edu.cn

基金项目: 国家自然科学基金(批准号: 12274042)和“111”计划(批准号: D21009, D17017)资助的课题.

Authors and contacts

1.
School of Photoelectric Engineering, Changchun University of Science and Technology, Changchun 130022, China

2.
Key Laboratory of Optoelectric Measurement and Optical Information Transmission Technology of Ministry of Education, Changchun University of Science and Technology, Changchun 130022, China

3.
Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Zhou Jian-Hong, zjh@cust.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 12274042) and “111” Program (Grant Nos. D21009, D17017).

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参考文献

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施引文献

图 1 (a) β-NaYF₄:Yb³⁺, Er³⁺ SEM图, 插图显示980 nm激光激发下纳米颗粒溶液的上转换发光照片; (b) NaYF₄:Yb³⁺, Er³⁺的TEM图; (c) NaYF₄:Yb³⁺, Er³⁺的HRTEM图, 插图为NaYF₄:Yb³⁺, Er³⁺的SAED图; (d) β-NaYF₄:Yb³⁺, Er³⁺ XRD谱图; (e)氧化电压40 V二次氧化时间 30 min 得D = 88 nm, P = 100 nm AAO的SEM图; (f) NaYF₄:Yb³⁺, Er³⁺填充AAO孔道结构SEM图; (g)结构示意图

Fig. 1. (a) Scanning electron microscope image of β-NaYF₄:Yb³⁺, Er³⁺, where the inset is up-conversion luminescence photo of nanoparticle solution under 980 nm laser excitation; (b) TEM diagram of NaYF₄:Yb³⁺, Er³⁺; (c) HRTEM diagram of NaYF₄:Yb³⁺, Er³⁺, illustration showing SAED diagram of NaYF₄:Yb³⁺, Er³⁺; (d) β-NaYF₄:Yb³⁺, Er³⁺ X-ray diffraction pattern; (e) the SEM images of D = 88 nm, P = 100 nm AAO obtained by oxidation voltage of 40 V and secondary oxidation time of 30 min; (f) SEM image of NaYF₄:Yb³⁺, Er³⁺ filled AAO pore structure; (g) structural diagram.

下载: 全尺寸图片幻灯片

图 2 (a)增强光谱图; (b) NaYF₄:Yb³⁺, Er³⁺/Al功率密度曲线; (c) NaYF₄:Yb³⁺, Er³⁺/AAO功率密度曲线

Fig. 2. (a) Enhanced spectral diagram; (b) NaYF₄:Yb³⁺, Er³⁺/Al power density curve; (c) NaYF₄:Yb³⁺, Er³⁺/AAO power density curve.

下载: 全尺寸图片幻灯片

图 3 (a)吸收光谱图; (b)波长980 nm近场增强图像

Fig. 3. (a) Absorption spectrogram; (b) near-field enhancement image with wavelength 980 nm.

下载: 全尺寸图片幻灯片

图 4 (a)测试光路示意图; (b) AAO增强NaYF₄:Yb³⁺, Er³⁺的红绿上转换发光对入射角度的依赖关系; (c) FDTD仿真模拟计算不同入射角下NaYF₄:Yb³⁺, Er³⁺/AAO吸收曲线; (d) NaYF₄:Yb³⁺, Er³⁺/AAO的980 nm, 650 nm, 540 nm电场增强因子与入射角度的关系

Fig. 4. (a) Test optical path schematic; (b) the dependence of the red-green up-conversion luminescence of NaYF₄:Yb³⁺, Er³⁺/AAO on the angle of incidence; (c) the absorption curves of NaYF₄:Yb³⁺, Er³⁺/AAO at different incidence angles calculated by FDTD simulation; (d) 980 nm, 650 nm, 540 nm electric field enhancement factor vs. incidence angle curve of NaYF₄:Yb³⁺, Er³⁺/AAO.

下载: 全尺寸图片幻灯片

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[3]	Zhang J, Shen H O, Guo W, Wang S H, Zhu C T, Xue F, Hou J F, Su H Q, Yuan Z B 2013 J. Power Sources 226 47 Google Scholar
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[6]	Janjua R A, Iqbal O, Ahmed M A, Al-Kahtani A A, Saeed S, Imran M, Wattoo A G 2021 RSC Adv. 11 20746 Google Scholar
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[16]	Chu A, He H, Yin Z, Peng R, Yang H, Gao X, Luo D, Chen R, Xing G, Liu Y J 2020 ACS Appl. Mater. Interfaces 12 1292 Google Scholar
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[22]	Li C, Quan Z, Yang P, Huang S, Lian H, Lin J 2008 J. Phys. Chem. C 112 13395 Google Scholar
[23]	Tang H, Xu Y, Cheng X 2020 J. Solid State Chem. 285 121229 Google Scholar
[24]	Bhiri N M, Dammak M, Carvajal J J, Aguiló M, Díaz F, Pujol M C 2022 Mater. Res. Bull. 151 111801 Google Scholar
[25]	Zhan S, Wu X, Tan C, Xiong J, Hu S, Hu J, Wu S, Gao Y, Liu Y 2018 J. Alloys Compd. 735 372 Google Scholar

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基于阳极氧化铝模板增强NaYF₄:Yb³⁺/Er³⁺上转换发光研究